Environmental Pollution 158 (2010) 11051118

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Review

Possible treatments for arsenic removal in Latin American waters for human consumption
Marta I. Litter a, b, c, *, Maria E. Morgada b, Jochen Bundschuh d, e
a

mica, Centro Ato mico Constituyentes, Comisio n Nacional de Energ a Ato mica, Av. Gral. Paz 1499, CP 1650, San Mart n, Prov. de Buenos Aires, Argentina Gerencia Qu cas y Te cnicas, Av. Rivadavia 1917, CP 1033, Ciudad de Buenos Aires, Argentina Consejo Nacional de Investigaciones Cient c n e Ingenier a Ambiental, Universidad Nacional de Gral. San Mart n, Peatonal Belgrano 3563, 1 piso, CP 1650, San Mart n, Prov. de Buenos Aires, Argentina Instituto de Investigacio d University of Applied Sciences, Institute of Applied Research, Moltkestr. 30, 76133 Karlsruhe, Germany e Department of Earth Sciences, National Cheng Kung University, University Road, Tainan City 701, Taiwan
b

Low-cost techniques should be urgently investigated to remove arsenic in drinking water in poor disperse rural and urban Latin American populations.

a r t i c l e i n f o
Article history: Received 12 December 2009 Received in revised form 25 January 2010 Accepted 31 January 2010 Keywords: Arsenic Latin America Removal technologies

a b s t r a c t
Considering the toxic effects of arsenic, the World Health Organization recommends a maximum concentration of 10 mg L1 of arsenic in drinking water. Latin American populations present severe health problems due to consumption of waters with high arsenic contents. The physicochemical properties of surface and groundwaters are different from those of other more studied regions of the planet, and the problem is still publicly unknown. Methods for arsenic removal suitable to be applied in Latin American waters are here summarized and commented. Conventional technologies (oxidation, coagulation coprecipitation, adsorption, reverse osmosis, use of ion exchangers) are described, but emphasis is made in emergent decentralized economical methods as the use of inexpensive natural adsorbents, solar light technologies or biological treatments, as essential to palliate the situation in poor, isolated and dispersed populations of Latin American regions. 2010 Elsevier Ltd. All rights reserved.

1. The problem of arsenic in Latin America (LA) As it has been largely reported, water pollution by arsenic is a worldwide problem with high impact mainly in the poorest regions of the Planet. Arsenic is classied as a Group I carcinogen (human carcinogen, IARC, 2004) and severe health effects have been observed in populations all over the world drinking arsenicrich water over long periods (EPA, 2006). The permanent ingestion of waters with high arsenic concentrations provokes the appearance of arsenicosis, an illness with high incidence in Asia and LA; in LA, the disease is named Chronic Endemic Regional Hydroarsenicism (in Spanish: HACRE). Symptoms of this illness are palmplantar hyperkeratosis, damage to the central neural system, hepatic damage, hair loss, skin cancer and cancer of internal organs (lungs, liver, kidney and bladder). So far, there is no treatment for HACRE, and prevention is the only way to combat the illness, which

mica, Centro Ato mico Constituyentes, * Corresponding author at: Gerencia Qu n Nacional de Energ a Ato mica, Av. Gral. Paz 1499, CP 1650, San Mart n, Comisio Prov. de Buenos Aires, Argentina. Tel.: 54 11 6 772 7016; fax: 54 11 6 772 7886. E-mail address: litter@cnea.gov.ar (M.I. Litter). 0269-7491/$ see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.envpol.2010.01.028

involves reduction of As concentration in water or avoidance of people to As exposure (Das et al., 1996). Arsenic is widely distributed in soils, water, air and biota (especially marine species). It is a component of more than 200 different minerals, as arsenates, suldes, sulfosalts, arsenides, arsenites, oxides, silicates and elemental arsenic (Onishi, 1969; Yan Chu, 1994). Speciation of the element is a key factor in controlling mobility, availability and toxicity of arsenic in natural environments. Arsenic appears in inorganic as well as organic species, and the main oxidation states are III and V, depending on pH and redox properties of the media. Inorganic species (iAs) are much more toxic in general than organic arsenical compounds, and iAs(III) species are of great environmental concern in view of a combination of high mobility and toxicity in comparison with the pentavalent species, which can be more easily adsorbed and retained by different surfaces. Arsenic occurrence and mobilization takes place through a combination of natural processes (e.g., weathering reactions, biological activity, volcanic emissions, etc.). Although natural arsenic is the main source of pollution, anthropogenic activities account for a widespread As contamination, arising from a variety of industrial processes (mining, electrolytic processes, combustion of fossil fuels, wood preservation, urban wastes, medicinal use, sewage sludges, fertilizers, pigments,

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biocides, crop desiccants, glass, alloys, electronics, etc.) (Jacks and Bhattacharya, 1998; Juillot et al., 1999; Mulligan et al., 2001; Smedley and Kinniburgh, 2002). Keeping in view the toxic effects of inorganic arsenic on humans and other living organisms, the World Health Organization (WHO) recommends a limit of 10 mg L1 of arsenic in water for human consumption (World Health Organization, 2004). This guideline is based on a 6 104 excess skin cancer risk, which is 60 times higher than the factor typically used to protect public health (US Environmental Protection Agency, 1988). According to this value, the presence of arsenic in water for human consumption affects potentially around 140 million people (Ravenscroft et al., 2009). Four million of them were documented in LA according to the old regulation (50 mg L1, Bundschuh et al., 2009); however, in line with the new guidelines, much more people could be at risk. In South America, especially in Argentina, Chile and Peru, the problem is known since several decades ago, affecting mainly urban and rural poor populations not connected to drinking water networks. Due to the ample extension of the territory and the amount of people living there, the problem of As in LA reaches the same order of magnitude as in other regions of the world, such as SE Asia. As we will see in Section 2, various studies have been undertaken by local researchers, leading to suitable treatment methods. However, technologies have been not yet commercialized due to a lack of interest of authorities, local industries and international agencies for nancial and technical cooperation. Excellent publications can be found on the (bio)geochemical origin of arsenic in the various occurrences and effects on health (among others: Bundschuh et al., 2008, 2009; Hopenhayn-Rich et al., 1996; Ravenscroft et al., 2009). In consequence, this topic will be not addressed in this review and only some brief details will be given. A special mention should be made to IBEROARSEN (IBEROARSEN network, http://www.cnea.gov.ar/xxi/ambiental/ iberoarsen/default.asp), a thematic network sponsored by CYTED1) joining 46 groups of experts of 17 Iberoamerican countries, which handles the problem of arsenic in Iberoamerica from three points of view: 1) distribution of arsenic, 2) analytical methodologies, 3) removal technologies. It the web page recent information about the arsenic problem in the region, including a database on As occurrence can be consulted. Ravenscroft et al. (2009) dene four affected regions in South and Central America: the high volcanic mountains of the Andes, the arid Pacic coastal plains, the tropical river basins of Amazonia, and the semiarid Chaco-Pampean plain. Relevant data are also reported in publications of groups belonging to IBEROARSEN (Bundschuh et al., 2008, 2009). As an example, in Argentina, the regions with the highest arsenic contents in waters belong to the ChacoPampean plain (w1 106 km2), Puna and Cuyo; other areas are still under investigation (Bhattacharya et al., 2006; Blanco et al., 2006; Bundschuh et al., 2008, 2009; Litter, 2002, 2006a,b; Litter nez Gonza lez, 2004; Litter and Mansilla, 2003; Smedley and Jime et al., 2002). Arsenic content (mainly As(V)) varies largely, between 4 and 5300 mg L1; a value of 14 969 mg L1 was reported recently in the Santiago del Estero province (Bhattacharya et al., 2006). In some places, 99% of groundwaters exceed the guideline of 10 mg As L1. In the north of Chile (Atacama Desert, from Arica to Antofagasta, approximately 250000 km2), worrying levels of arsenic in drinking water are present, with concentrations 6300 times higher than the limit recommended by the WHO (Bundschuh

nez et al., 2008, 2009; Litter, 2002, 2006a,b; Litter and Jime lez, 2004; Litter and Mansilla, 2003). In Brazil, one of the Gonza most problematic zones is the large mining region belonging to the Minas Gerais state, known as the Iron Quadrangle, where values of As in waters up to 2980 mg L1 have been measured; high concentrations have been also found in Ribera valley and in the Amazonic region (Borba et al., 2003; Bundschuh et al., 2008, 2009; Matschullat et al., 2000). Arsenic in Bolivia is present mostly in the occidental Andean region (in the As-Ag-Pb-Zn-Cu-Au belt), where lake (central values up to 4800 mg L1 have been found in the Poopo Andes) and other places (Bundschuh et al., 2008, 2009; Matschullat xico, the rst cases of arsenicosis were identied et al., 2000). In Me in 1958 in the Comarca Lagunera (Durango and Coahuila states), where values higher than 700 mg As L1 were found in waters n et al., 1994). In Zimapa n (Bundschuh et al., 2008, 2009; Cebria (Hidalgo state), and in Chihuahua and Sonora states, concentrations up to ca. 6000 mg L1 have been found, many of them related to vez et al., 2000). In Nicaragua, the rst cases of mining (Carrillo-Cha hydroarsenicism were identied in 1996 in El Zapote (Matagalpa), and many sources of drinking water in the zone present nowadays high concentrations, with a reported value of 1320 mg L1 (Bundschuh et al., 2008). In El Salvador, arsenic pollution is amply distributed in surface, groundwaters and sediments, with high concentrations informed in the Olomega lake (4200 mg L1) and in other regions (Bundschuh et al., 2008). In Costa Rica, concentrations up to 30 000 mg L1 were found in geothermal reservoirs and up to 2000 mg L1 in hot spring waters (Bundschuh et al., 2008). Investigations are underway or even pending in Uruguay, , Ecuador, Cuba, Honduras, Repu blica Dominicana, Paraguay, Peru Colombia and Venezuela, (Bundschuh et al., 2008, 2009; Castro de Esparza, 2003; Litter, 2006a; Matschullat et al., 2000; Smedley and Kinniburgh, 2002), where the presence of arsenic in groundwaters can be foreseen due to geological features. Recent data can be obtained from the IBEROARSEN web site (IBEROARSEN Network, http://www.cnea.gov.ar/xxi/ambiental/iberoarsen/default.asp; Morgada et al., 2008). This short overview only aims to point out that the degree of knowledge about arsenic concentrations in groundwater is still not complete in LA, and much more efforts are mandatory to complete the map of arsenic distribution, extending the study to soils and sediments. 2. Technologies for arsenic removal: which can be suitable for LA? Arsenic removal from waters is not an easy task. Economical aspects are perhaps the most important factors for the selection of the technology, taking into account size of the population, incidence of chronic illnesses, lack of safe water, poverty conditions, and other socioeconomic variables. In most cases, sophisticated, expensive techniques cannot be applied in populations with low economical resources. In addition, arsenic treatment units require very sensitive monitoring and maintenance arrangements, which falls far beyond the economic scope of poor isolated communities. Moreover, a number of cultural and political factors play deciding roles in the implementation of new technologies (Kemper and Minnatullah, 2005). It is necessary to remark that either to evaluate arsenic contents in waters and soils or to select a removal technology, it is essential to have suitable methodologies for quantitative measurement of low arsenic concentrations, mainly due to the low detection and levels that must be attained. Speciation and development of cheap in-eld technologies are also needed. These issues are beyond the scope of this article, but the interested readers can consult an excellent comprehensive review (Francesconi and Kuehnelt, 2004). IBEROARSEN has also recently published in Spanish a volume

1 CYTED, Science and Technology for the Development, is an organization of 21 Iberoamerican countries, nanced by the Spanish Government and the National Science and Technology Agencies of Portugal and Latin American nations.

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devoted to this topic (Litter et al., 2009; IBEROARSEN Network, http://www.cnea.gov.ar/xxi/ambiental/iberoarsen/default.asp). From a technical point of view, the physicochemical and microbiological characteristics of the waters and the available materials in the region will determine the most convenient technology for removal of arsenic in each site. The selection of the method depends greatly on arsenic speciation, chemical composition of the water, reduction potential, hardness, presence of silica, sulfate, phosphate, iron and other chemical species, volumes to be treated and degree of sophistication that may be applied. Kartinen and Martin (1995) stated that many of the existing processes are acceptable under the correct circumstances, but the challenge is to determine which process goes with which set of circumstances. We should add that, sometimes, the removal technology is suitable, but its application is not possible due to the reluctance of people to accept the changes on the organoleptic properties of waters they have been drinking for years. Additionally, the volume, handling and nal disposal of the generated wastes should be considered, but this aspect will be not treated here. Important references can be consulted (Hering et al., 1997; McNeill and Edwards, 1995; Meng et al., 2000; Sancha, 2003). All technologies rely on a few basic chemical processes that can be applied alone, simultaneously or in sequence: oxidation/reduction, coagulationltration, precipitation, adsorption and ion exchange, solid/liquid separation, physical exclusion, membrane technologies, biological methods, etc. Most arsenic removal technologies are efcient when the element is in the pentavalent state, because it is present in the form of oxianions, mainly H2AsO 4 and HAsO2 4 , in a pH range of 212, while the trivalent form is uncharged at pH below 9.2 (H3AsO3). This is the reason why many arsenic remediation methods use, previously to other processes, an oxidation step. However, oxidation without help of other physical or chemical transformations does not remove arsenic from water. As it is obvious, boiling of water for purication does not remove arsenic and, on the contrary, this process increases As concentration by evaporation. This is a fact commonly ignored by the potentially affected people. For previous reports on arsenic removal, see for example Feroze ller, 2008; Pirnie, 2000. Ahmed, 2002; Newcombe and Mo Comprehensive revisions, covering other complementary aspects, can be found in Ravenscroft et al. (2009) and in Sharma and Sohn (2009). In what follows, conventional, well-established technologies for arsenic removal will be briey mentioned. Emergent technologies will be addressed in more detail later, with emphasis on those methodologies that could be suitable for application in poor, isolated, decentralized rural and urban populations of LA, not connected to water network distribution. 2.1. Conventional technologies The most common technologies include processes that can be used alone or in combination, such as oxidation, coprecipitation and adsorption onto coagulated ocs, lime treatment, adsorption onto suitable surfaces, use of ion exchange resins and membrane ller, 2008; Ravenscroft et al., technologies (Newcombe and Mo 2009; Sharma and Sohn, 2009). Most of them are condent and well understood technologies for arsenic removal in large and medium scale treatment plants for centralized services. 2.1.1. Oxidation and reduction Oxidation is a previously required step to transform As(III) species in more easily removable As(V) species. Simple direct aeration is slow (Bissen and Frimmel, 2003), but a number of chemicals, including gaseous chlorine, hypochlorite, ozone,

permanganate, hydrogen peroxide, manganese oxides and Fentons reagent (H2O2/Fe2) can be employed to accelerate oxidation (see Feroze Ahmed, 2002; Pirnie, 2000). Chlorine is a rapid and effective oxidant, but it may react with organic matter, producing toxic and carcinogenic trihalomethanes as by-products. Potassium permanganate effectively oxidizes arsenite, and it may be a widely available inexpensive reagent suitable for developing countries. Hydrogen peroxide can be an effective oxidant if the raw water contains dissolved iron, which often occurs in conjunction with arsenic contamination, allowing the occurrence of Fenton reactions (see Section 2.2.6). Ultraviolet radiation alone or with suitable light absorbers such as TiO2 can be also convenient options for As(III) oxidation (see Section 2.2.6). 2.1.2. Precipitation Methods taking advantage of the insolubility of certain arsenical inorganic compounds such as As(III) sulde, calcium arsenate and ferric arsenate may be proposed to remove As from water. By adding calcium, magnesium, manganese (II) or iron (III) salts to As(V) solutions, As-containing solids are obtained that can be removed through sedimentation or ltration. However, the method is generally not suitable because of the instability of most of the solids, also inadequate for direct disposal, although it can be used to palliate the problem in mining sites where those salts are present naturally (Ladeira et al., 2002). The solubility of the different materials is very dependent on their nature, pH and other variables, and the aqueous solutions in equilibrium with the metal arsenates have extremely high arsenic concentrations, exceeding the guidelines for drinking waters and even for sewage efuents and wastes es, 2002; Ravenscroft et al., 2009; (Bothe and Brown, 1999; Magalha Vogels and Johnson, 1998). 2.1.3. Coagulation and ltration The most common technology for arsenic removal is coagulation and ltration. Arsenic is removed in the pentavalent form, which adsorbs onto coagulated ocs and can be then removed by ltration. As(III) has to be previously oxidized, generally with chlorine (Kartinen and Martin, 1995). The most used coagulants are aluminum sulfate (Al2(SO4)3), iron chloride (FeCl3) and ferrous sulfate (FeSO4), iron salts being generally better removal agents. FeCl3 generates relatively large ocs, while smaller ones are formed with FeSO4 (Edwards, 1994; Hering et al., 1997; Newcombe and ller, 2008; Pirnie, 2000; Ravenscroft et al., 2009). Mo Filtration is a necessary step. Without ltration, arsenate removal is around 30%, but using a 0.1 or 1.0 mm lter, arsenate removal improves to more than 96% (Hering et al., 1996; Chwirka et al., 2000; Fields et al., 2000; Jekel and Seith, 2000; Madiec et al., 2000; Sancha, 1999, 2000). The coagulationltration technology is simple, only common chemicals are used, installation costs are small and it can be easily applied to large water volumes. However, relatively large volumes of As-containing sludges are formed, typically disposed off in landlls, and being a potential source of contamination. In Chile, some plants based on the coagulation technology were implemented in the 70s, constituting a great solution for the problem of arsenic for small and medium cities (Sancha and Ruiz, 1984; Sancha, 1999, 2000, 2003, 2006; Sancha and Fuentealba, 2009). The rst plant, using direct ltration and FeCl3 as coagulant was installed in 1970 in Antofagasta (El Salar del Carmen complex). Other As removal plants are those of Chuquicamata (Sancha, 2006) and Taltal (Sancha, 2006; Sancha and Fuentealba, 2009). In Argentina, the Center of Sanitary Engineering of the National a Sanitaria de la University of Rosario (Centro de Ingenier

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Universidad Nacional de Rosario) developed the ARCIS-UNR process, which uses a coagulationadsorption method with polyaluminum chloride (PAC) or ferric chloride, followed by a double ltration. The technology proved to achieve 8090% of As removal (Ingallinella et al., 2003a,b; Ingallinella, 2006; Litter et al., 2008). Later, various small and medium plants have been successfully implemented in the country with this methodology. 2.1.4. Lime softening In the presence of water and carbonic acid, lime forms calcium carbonate, and can be used to adsorb arsenic, the process ending with a coagulation step. The method is efcient to treat water with high hardness, especially at pH > 10.5. Addition of chlorine to oxidize As(III) is needed. The disadvantages are: 1) a very high pH in the resulting water (1012), which implies a further acidication step; 2) a very high dose of coagulant is needed; 3) relatively low removal efciencies (generally not less than 1 mg L1), secondary treatments being required (Fields et al., 2000; Kartinen and Martin, 1995; ller, 2008; Pirnie, 2000; Ravenscroft et al., 2009). Newcombe and Mo 2.1.5. Adsorption Aluminum oxides (activated alumina), iron oxide/hydroxides, titanium dioxide, cerium oxide, or reduced metals can be used as adsorbents (Ravenscroft et al., 2009). Granular activated alumina (Al2O3/Al(OH)3) is a commercially available porous oxide, successfully applied at slightly acid pH (57), giving efciencies higher than 95% for both As(V) and As(III) (Pirnie, 2000). The technology is very simple, does not require chemical addition and is useful at community or household levels. Granular iron hydroxide, GFH, a synthetic akaganeite, proved to be a good material, able to retain As(V) and As(III) (Driehaus, 2002; Hering et al., 1997; Wang et al., 2000). Granular iron oxide (Bayoxide, GFO) is another similar successful material, containing less than 70% of Fe2O3 (Severn Trent Services, 20072009). Commercial titanium dioxide (Bang et al., 2005b; Dow Chem, 2005), cerium oxide (Shimoto, 2007; Amimono, 2007) and manganese dioxide (Driehaus et al., 1995) proved to be also effective. Microparticles with magnetic properties were developed to remove the adsorbent material after the treatment (Dahlke et al., 2003). In another design, iron hydroxide nanoparticles were introduced into a polymeric network of ionic exchange resin. The materials were tested with good results in arsenic-contaminated groundwater of a village bordering Bangladesh and India (Cumbal and SenGupta, 2009; DeMarco et al., 2003). Very cheap materials were developed using sand and quartz covered by metallic oxides and their use as emergent materials will be described in Section 2.2.4. However, despite their simplicity, the adsorption methods usually fail in lowering arsenic concentration to acceptable levels, and are recommended to treat only water with low Fe/As content (Chaudhury et al., 2003; Driehaus et al., 1995). The alumina surface is saturated very rapidly at high As concentrations, and regeneration is necessary, usually with a caustic bath followed by an acid treatment (Kartinen and Martin, 1995). Efciencies are higher with As(V) than with As(III). 2.1.6. Membrane processes From the possible membrane processes, microltration (MF) or ultraltration (UF), which use low-pressure membranes (large nominal pore sizes, 1030 psi) are not completely adequate because the arsenical species are very small and can traverse the membranes. In contrast, nanoltration (NF) or reverse osmosis (RO), which use high-pressure membranes, 75250 psi, or even higher (Clifford, 1999; Pirnie, 2000); iii) electric repulsion by ller, 2008; Pirnie, 2000; membranes (Newcombe and Mo Ravenscroft et al., 2009), have appropriate pore sizes. In RO, an

external pressure is applied to reverse natural osmotic ow, and water ows from a more concentrated saline solution through the semipermeable membrane, which has a thin microporous surface that rejects impurities but allows water to pass through. The membrane rejects especially polyvalent ions, being suitable for arsenic oxyanions. The process is efcient over an extended pH range (311). Because in NF and RO only a small amount of the raw water (10 15%) passes through the membrane, these processes are suitable for household or applications where only a small amount of treated water is required. For higher water volumes (e.g., municipal systems), multiple membrane units in series have to be used (Pirnie, 2000). Operation and maintenance requirements for membranes are minimal: no chemicals are needed, and maintenance consists of only ensuring a reasonably constant pressure, and periodically cleaning of the membranes. The main disadvantages, especially for RO, are low water recovery rates (typically 1020%), high electrical consumption, relatively high capital and operating costs (expensive membranes), and the risk of membrane fouling. High concentrations of suspended solids, organic matter, humic acids, hardness, suldes, ammonium, nitrite, methane, etc. interfere. Only low levels of arsenic can be treated. Discharge of rejected water (2025% of the inuent) or brine is also a concern; therefore, the technology is not useful in areas where water is scarce. The method provides good As(V) but poor As(III) removal, and oxidation is difcult because residual oxidants can damage the membranes (EPA, 2006). In addition, RO eliminates not only arsenic but also ions, altering the chemical composition or organoleptic properties of drinking waters. Several RO plants have been installed recently in Argentina, e.g. rdoba and La Pampa (DAmbrosio, in the provinces of Santa Fe, Co 2005). In electrodialysis (ED), ions are transported from a lesser to a higher concentrated solution through ion permeable membranes under the inuence of a direct electric current. The efciency of the technique is similar to that of RO, mainly in treating water with high total dissolved solids (TDS). Electrodialysis with reversion of polarity of the electrodes (EDR) is an improvement of ED with minimization of scaling (Pirnie, 2000; Ravenscroft et al., 2009). Garrido et al. (2008), developed capacitive deionization (CI), an advanced electrochemical method based on the deionization by ow through a capacitor like system with electrostatic load, congured as a low-cost lter of coal electrodes. This technology is recommended for water containing less than 3000 mg L1 of total dissolved solids. The advantages of capacitive deionization over RO, NF and electrolysis are: 1) smaller amount of chemical reagents for the cleaning of cells or membranes; 2) both As(V) and As (III) can be removed; 3) the volume of rejected water is low (between 3 and 7% of the treated volume); 4) low operative and maintenance costs. 2.1.7. Ion exchange resins Synthetic ionic exchange resins, generally of polymeric matrix (polystyrene cross-linked with divinylbenzene), linked to charged functional groups, can be applied for As removal; quaternary amine groups, N(CH3)3, are the preferred groups. Arsenate removal is efcient, producing efuents with less than 1 mg L1 of arsenic, while arsenite, being uncharged, is not removed, and a previous oxidation step is necessary (Pirnie, 2000; Ravenscroft et al., 2009). Commonly, resins are pretreated with hydrochloric acid, to establish chloride ions at the surface, which are easily displaced by arsenic. Arsenate removal is relatively independent of pH and inuent concentration. HAsO2 4 has adsorption ability higher than . Competing anions, especially sulfate, TDS, selenium, that of H2AsO 4 uoride, and nitrate, interfere strongly and can affect run length.

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Suspended solids, SS, and precipitated iron can cause clogging (Kartinen and Martin, 1995; Pirnie, 2000; Wang et al., 2000). The most important producers of ion exchanger materials (Purolite, Bayer, Dow Chem and Rohm and Haas) have introduced new tailored anionic exchangers to attain values below 10 mg L1. 2.1.8. Comparison of conventional technologies for As removal In Table 1 are compared the conventional technologies with their advantages and disadvantages. 2.2. Emergent technologies In the last decades, a large amount of scientic and technological work has been devoted to develop new technologies for arsenic remediation that seek to minimize costs of investment, operation and maintenance (i.e., low-cost technologies) and technological development (i.e., low-tech systems). These technologies focus more on small scale or household treatments for isolated populations. However, the social acceptance, waste production and treatment and the corresponding required handling needs to be assessed before considering the implementation of each remediation option. Some of these technologies are merely adaptation of conventional methods like coagulationltration, or adsorption, using very cheap materials (iron-coated sand, bricks, iron lings, activated alumina or carbon) to be employed at household or community scale (Kemper and Minnatullah, 2005; Ravenscroft et al., 2009). 2.2.1. In-situ remediation In-situ based technologies have lower operation costs in comparison with on-site or off-site treatment as the classical pump and treat technologies. Different approaches have been applied by bioremediation, permeable reactive barriers, air dispersion, chemical oxidation, multiphase extraction, supervised

natural attenuation, etc. Biological methods will be reviewed in Section 2.2.5. The use of permeable reactive barriers (PRB) and reactive zones has been postulated as one of the most efcient technologies for insitu removal of pollutants, particularly for As from groundwater. Fe (or Al) oxide-containing materials can be used as relatively cheap passive reactive barriers (Bhattacharya et al., 2002; Gavaskar et al., 1998; Gu et al., 1999; Lindberg et al., 1997). In PRB technology, a reactive medium is interposed in the way of the contaminant plume as shown in Fig. 1. The appropriate reactive material is able to induce physicochemical and/or biological processes to remediate groundwater contamination. PRBs are particularly attractive for decontamination of groundwater because they are less expensive than conventional technologies and no costly equipments for operation are needed. The involved main processes are sorption, precipitation, chemical reaction and/or biogenic reactions (Diels et al., 2003). For arsenic, PRBs should be built by materials that enable adsorption and/or coprecipitation of the anionic species, such as mixtures of iron oxides with silica and calcite (Lackovic et al., 2000). Important drawbacks of the technology are: 1) high impact of long-term microbiological and geochemical processes on the durability of the barrier, 2) degradation of the material by corrosion and 3) decrease of permeability by precipitation of suldes, oxides, hydroxides and carbonates. The technology has been directed recently to the use of zerovalent iron (ZVI), as a new sorption medium to remove both arsenate and arsenite; values always below 10 mg L1 are achieved (Gibert et al., 2003a,b; Su and Puls, 2001, 2003). In form of columns, it can be applied directly for household applications (see Section 2.2.3). 2.2.2. Combined coagulation/occulation and adsorption methods Different technologies for single households were developed or adapted by scaling down and simplifying conventional methods

Table 1 Advantages and disadvantages of conventional technologies for arsenic removal. Technologies Oxidation and reduction Advantages Simple. Small installation costs. Easily applied to large water volumes. Arsenite can be directly oxidized by a number of chemicals and/or UV light. Solid obtained can be removed through sedimentation and ltration. Simple. Easily applied to large water volumes. Effective when As(V) is the only pollutant. Low capital and operative costs. Alum allows F removal. Disadvantages Some oxidants produce toxic and carcinogenic by-products. Needs further removal treatment. Solids rather unstable and inadequate for direct disposal as they will produce As-containing liquid residues. Low removal efciency. pH needs adjustment. Disposal of the arsenic-contaminated coagulation sludge may be a concern. Low removal efciency. Filtration needed. As(III) must be previously oxidized. Low efciency. High coagulant dose. High pH in the efuent. May require secondary treatment. Moderate efciency. Regeneration needed. Interferences: Se, F, Cl and SO2 4 . Application of point-of-use treatment devices needs regeneration and replacement. Only low As levels can be treated. Poor As(III) removal. For high water volumes, multiple membrane units required. Low water recovery rates (1020%). High electrical consumption. High capital and operation costs. Membrane fouling. Many interferences. 2025% water rejection. Other ions can be removed. Very high costs.

Precipitation

Coagulation/ltration

Lime softening Adsorption (activated alumina, iron oxides/hydroxides, TiO2, cerium oxide, metals) Reverse osmosis and nanoltration

pH > 10.5 provides efcient As removal. Efcient to treat water with high hardness. Simple. Not other chemicals required. Highly selective towards As(V). Effective with water with high TDS. Useful at community or household levels. Useful at community or household levels. Minimal membrane operation and maintenance. Highly effective towards As, effective in treating water with high TDS

Electrodialysis, electrodialysis with reversion of polarity of the electrodes Ion exchange

Efciency similar to reverse osmosis, effective in treating water with high TDS. Minimize scaling by periodically reversing the ows of dilute and concentrate and polarity of the electrodes. Effective removal. Not pH and inuent concentration dependent.

As (III) is not removed. Sulfate, TDS, Se, F and NO 3 interfere. SS and precipitated iron cause clogging. May require pretreatment.

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Fig. 1. Conceptual scheme of PRBs.

used in water treatment plants, which use the oxidation, adsorption and coagulation sequence for As removal from drinking water (Sastre et al., 1997; Castro de Esparza and Wong de Medina, 1998). A household scale low-cost As removal methodology was developed in Peru (Castro de Esparza et al., 2005) using ALUFLOC, a mixture of an oxidant (chlorine), activated clays (acting as As adsorbents and/or ion exchangers) and a coagulant (Al2(SO4)3 or FeCl3) (Bedolla et al., 1999). This methodology was tested in Puno and allowed to remove up to 98% of the dissolved As (As concentration in raw water: 1 mg L1); at higher As concentrations, the removal efciency decreased. The suitability of an activated aluminum hydroxide hydrogel, added directly to the water, for use at household scale was tested n, 2001). The hydrogel was (Lujan and Graieb, 1994, 1995; Luja prepared using hydrated aluminum sulfate, powdered calcium hypochlorite, ammonium hydroxide and demineralized water. Two hundred groundwater samples (40800 mg L1 As) from different n province (Argentina) were tested, attaining wells of the Tucuma nal As concentrations below 10 mg L1 in all cases. 2.2.3. Zerovalent iron Zerovalent iron is an emergent material increasingly used for the treatment of several pollutants, particularly toxic metals. As said before, ZVI is one of the main components of PRBs. In last times, arsenic removal with ZVI has been object of different studies (Kanel et al., 2005; Leupin et al., 2005; Leupin and Hug, 2005; Manning et al., 2002; Su and Puls, 2001). The method is useful for both As(V) and As(III). In the case of As(III), removal by ZVI takes place mainly by adsorption and coprecipitation onto iron hydroxides or oxides formed during ZVI oxidation (Bang et al., 2005a; Kanel et al., 2005; Lackovic et al., 2000). The mechanism involves preliminary Fe(0) corrosion: ZVI oxidation in the presence of water and oxygen produces Fe(II) and then different Fe(II)/(III) oxides or hydroxides such as iron rusts, magnetite, lepidocrocite, maghemite, ferrous hydroxide ferric hydroxide, etc., depending on redox conditions and pH: 2Fe0 D 2H2 O D O2 / 2FeII D 4OHL (1)

L 2O D 2HD / H2 O2 D O2 2 L / HO D O2 D HOL H2 O2 D O 2 L FeII D O D 2HD / FeIII D H2 O2 2

(4) (5) (6) (7)

FeII D H2 O2 / FeIII D HO D HOL Fenton reaction

Species of higher oxidation state, like Fe(IV), were also proposed to be formed, especially at neutral pH. Recently, Ramos et al. (2009) studied the mechanism of As immobilization on nanoparticulate ZVI (NZVI) using High Resolution X Ray Photoelectronic Spectroscopy (HR-XPS) and informed clear evidence of As(0) formation together with As(III) and As(V) on the nanoparticle surface after reaction with As(III) or As(V) in solution. These results proved that both reductive and oxidative mechanisms take place during NZVI treatment. The dual function exhibited by NZVI is possible by the core-shell structure of NZVI, which contains a highly reducing metal core and a thin layer of amorphous iron oxyhydroxide, promoting coordination and oxidation of As(III). According to Leupin and Hug (2005), the application of metallic iron to remove arsenic from waters is promising for several reasons: i) metallic iron is widely available and iron lings can be produced locally even in poor localities at low-cost, ii) iron corrosion converts iron to strongly sorbing iron oxides, iii) the reactive intermediates formed during corrosion of metallic iron in aerated waters oxidize As(III) to As(V), iv) the combination of As(III) oxidation and sorption of As(V) makes unnecessary the use of oxidizing chemicals. There are already results of laboratory experiments with zerovalent iron, which use cartridges lled with sand, local iron materials, iron wool and packing wire, as well as iron nanoparticles (NZVI) (Bundschuh et al., 2009; Leupin et al., 2005; Litter, 2006a,b; nez Gonza lez, 2004; Litter and Litter et al., 2008; Litter and Jime Mansilla, 2003; Morgada et al., 2008, 2009; Morgada de Boggio et al., 2009, in press; Su and Puls, 2001). A recent work was performed recently in Argentina with commercial nanoparticles produced by a local industry. A rapid As(V) removal using very low iron concentrations (0.0050.1 g L1) took place, attaining more than 90% after 150 min of contact time at the optimal NZVI concentration. The commercial NZVI presented an outstanding ability to remove As from waters from the Chaco-Pampean plain, due not only to a high surface area and low particle size but also to a high intrinsic activity. Irradiation strongly improved As removal in natural waters, and this aspect will be described in Section 2.2.6.

Once formed, Fe(II) reacts with dissolved O2 generating Reactive  Oxygen Species (ROS) like HO, O 2 /HO2, H2O2, and it is oxidized to Fe(III), according to the following simplied equations at neutral pH (Hug and Leupin, 2003; Joo et al., 2004; Leupin and Hug, 2005; Morgada et al., 2009; Voegelin and Hug, 2003).
L FeII D O2 / FeIII D O 2

(2)

L FeII D O D 2HD / FeIII D H2 O2 2

(3)

M.I. Litter et al. / Environmental Pollution 158 (2010) 11051118

1111

A method using electrochemical corrosion of a xed bed of metallic iron was developed and applied in San Juan, Argentina ceres, 2007; Litter et al., 2008). The procedure is ideal to be (Ca applied on a small scale (household to few hundred people) and consists of a rst oxidative chlorination step, a second step using a bed lled with iron llings or small pieces of iron, conditioning of the ocs and ltration. Removals above 90% were obtained. 2.2.4. Geological materials as natural adsorbents and other low-cost materials Remediation with natural geological materials (soils or sediments) is an emerging solution for poor people in remote rural settlements at household level, especially if the materials are locally available and can be collected by the population. Various natural Feand Al-rich minerals such as hematite (a-Fe2O3), goethite (aFeO(OH)), gibbsite (g-Al(OH)3) and soils or sediments including these minerals (e.g., oxisols, laterite), indigenous limestone (Soyatal), iron-coated zeolites, clay minerals (montmorillonite, bentonite) were tested either with laboratory-prepared or natural waters, and identied as alternative adsorbents for small water volumes (Alvarez-Silva et al., 2009; Armienta et al., 2009; Bhattacharya et al., 2002; Castro de Esparza and Wong de Medina, 1998; Claesson and Fagerberg, 2003; Deschamps et al., 2003, 2005; Litter, 2006a,b; nez Gonza lez, 2004; Litter and Mansilla, 2003; Litter and Jime oz Ladeira and Ciminelli, 2004; Mellano and Ramirez, 2004; Mun a, 2000; Simeonova, 2000; Storniolo et al., 2005; Rivera and Pin et al., 2005; US Environmental Protection Agency, 2002; Weerasooriya et al., 2003). Materials based on iron/manganese oxides, like greensand and other various natural minerals, have been also investigated (Deschamps et al., 2005; Mohan and Pittman, ller, 2008; Pirnie, 2000; Prasad, 1994; 2007; Newcombe and Mo Shevade and Ford, 2004; Zeng, 2003). Simple sand lters can be a very feasible option for As removal from groundwater exhibiting iron concentrations up to around 400 mg L1. The method has been proved efcient in Vietnam at household level (Luzi et al., 2004). Interesting materials to remove As at small scale were iron oxide coated sand (IOCS) (Bhattacharya et al., 2002; Chen et al., 2004; Deschamps et al., 2005 Joshi and Chaudhury, 1996; Thirunavukkarasu et al., 2004), manganese dioxide coated sand (Bajpai and Chaudhury, 1999) and limestone particles covered by iron oxide (Banavali et al., 2008). 2.2.5. Biological methods Relatively little is known about the use of biological removal of arsenic from water, although these methods show a great potential due to its environmental compatibility and possible costeffectiveness. Microbial activity can remove, mobilize, and contain arsenic through sorption, biomethylationdemethylation, complexation, coprecipitation, and oxidation-reduction processes. Ex-situ bioleaching can effectively remove arsenic from contaminated soils, helped by biostimulation, e.g., addition of carbon sources and mineral nutrients. Bioadsorption, i.e., adsorption of pollutants by a biomass or biolm of living or dead organisms such as algae, bacteria, aquatic macrophytes or vegetal organisms and biopolymers, can be used either ex-situ or in-situ; coprecipitation with biogenic solids or suldes can be also tried. Both As(III) and As(V) can be efciently adsorbed and precipitated onto biological ocs built by iron bacteria (Katsoyiannis and Zouboulis, 2004a,b; Teixeira and Ciminelli, 2005; Wang and Zhao, 2009). Recent reviews are available (Lasat, 2002; Cherian and Oliveira, 2005; Dickinson et al., 2009). In LA, different types of low-cost natural biological materials such as cellulose, milled bones, sedges, sorghum biomass, waste biomass, and others have been tested for their suitability to remove

iz et al. (2009) developed lters for As removal As from water. Mun using a combination of cellulose and activated carbon from lignite as adsorbents. Another interesting approach was that of Teixeira and Ciminelli (2005), who tested activated waste biomass with high brous protein content (rich in keratin) obtained from chicken feathers. The method allowed selective adsorption of As(III) at low pH with sorption rates up to 270 mmol As(III) g1 of biomass. Natural biogenic hydroxyapatite (HAPb) obtained from cowcharred bones resulted a good sorbent for As(V) in water under the conditions explored by the authors (1000 mg L1, 5 g L1 adsorbent, circumneutral pH, 24 h contact time, Czerniczyniec et al., 2007). Phytoltration, i.e., the use of plants to remove contaminants from water, is another emerging technology. Huang et al. (2004) investigated the potential of two hydroponically cultivated arsenic hyperaccumulating ferns (Pteris vittata and Pteris cretica cv. Mayii) to remove As (20500 mg L1). As examples, P. vittata reduced As concentration from 200 to 2.8 mg L1, and from 20 mg L1 to 0.4 mg L1 in 24 h. Interestingly, the authors claim that the phytoltration technique may provide the basis for a solarpowered hydroponic technique to treat arsenic-contaminated drinking water at small scale. Alvarado et al. (2008) studied As removal (0.15 mg L1) by Water Hyacinth (Eichhornia crassipes) and Lesser Duckweed (Lemna minor). No signicant differences were found between both species on bioaccumulation capability. The removal rate for Water Hyacinth was higher than that of Lesser Duckweed, this species representing a reliable alternative for arsenic bioremediation in waters. Phytoremediation can be also performed using As-tolerant n-Herrera et al. (2009) evaluated the As plant species. Alarco tolerance of two Cyperaceae species, Schoenoplectus americanus and Eleocharis macrostachya, collected near the towns of Naica and , Chihuahua state, Mexico. Since 97% of the San Diego de Alcala plants survived the As exposure, and since plant growth was not visibly affected, it can be concluded that both species are tolerant to As and can be used for rhizoltration to remove As from drinking water. Hansen et al. (2004) studied As(V) biosorption using dried algae (Lessonia nigrescens) collected in Valparaiso bay, Chile. The experiments were performed using laboratory solutions (200 mg As(V) L1, pH 2.5, 4.5 and 6.5). Lessonia nigrescens showed very good adsorption capacities and its use may be interesting for small-scale drinking water treatment, deserving further investigation. Bundschuh et al. (2007) investigated the effectiveness and suitability of dried macro-algae (Spyrogira spp.) to remove As from lake acid mine drainage (AMD) and other waters from the Poopo basin (Bolivia, Andean highlands) nding higher efciency than that of typical plants like totora (Schoenoplectus californicus) and paja brava (Festuca orthophylla): 8090% of As removal was attained within 4 days. 2.2.6. Photochemical technologies Very cheap technologies based on the use of solar light, abundant in many regions where, at the same time, the problem of arsenic is dramatic, can be adapted for arsenic removal. The use of solar or articial light and dissolved iron has been object of several studies in the last decade, especially to facilitate oxidation of As(III) to As(V). Therefore, to effectively remove arsenic, a two-step process has to be designed: one for As(III) oxidation and the second one for elimination of the produced As(V). These two steps can be simultaneous or consecutive. Another possibility is the photochemical reduction of As(V) or As(III) to elemental As, a nonmobile, relatively stable As form, which can be, in this way, removed from the aqueous phase.

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2.2.6.1. As oxidation by light and chemical reagents. As said in Section 2.1.1, As(III) oxidation by atmospheric oxygen is thermodynamically possible but rather slow. The process can be accelerated under UV light irradiation, as described by Bissen et al. (2001): although no oxidation of As(III) (1 mg L1) was observed after one week in dark oxygenated aqueous solutions, irradiation with a solar simulator produced 54% of As(III) oxidation in 45 min. The authors attribute the acceleration to i) emission of the lamp at wavelengths under 280 nm, where As(III) presents some absorption, ii) the presence of contaminants at trace levels on the walls of the reactor, iii) a very weak absorbance of As(III) (e < 5 L mol1) at wavelengths over 289 nm; or iv) increase of the temperature. However, the use of direct UV illumination to promote As(III) oxidation has low efciency to guarantee its application in As removal. Addition of H2O2 to the UV system triggers As(III) oxidation. As already said in Section 2.1.1, H2O2 is a good oxidant for As(III) in the dark, but a large excess of peroxide is needed to achieve complete oxidation. In contrast, Yang et al. (1999) found that UV light promoted As(III) oxidation in the presence of H2O2. Complete oxidation of 525 mM As(III) (air-saturated solution at pH 9) took place in less than 10 min with low H2O2/As(III) molar ratios (from 2:1 to 1:4). The authors attribute the enhancement of As(III) oxidation to the occurrence of H2O2 photolysis, which generates powerful oxidants, the HO radicals: H2 O2 D hn / HO (8)

around 85 L of capacity for a solar process and (b) a reactor with 24 low-pressure mercury lamps (65 W). Arsenic oxidation was completed in around 16 h under solar light (MSE Final Report, 1997). The process was later adapted for a eld demonstration in Bangladesh (BGS Main report, 1999). Kocar and Inskeep (2003) evaluated the use of ferrioxalate under UV radiation for As(III) oxidation in an ample pH range (37). Photolysis of iron oxalate leads to CO 2 that, under aerobic conditions, reacts very quickly with O2, yielding superoxide radicals:
L L L FeIIIC2 O4 3 D hn / FeII D 2C2 O2 D C2 O 3 4 4 L L / CO D CO2 C2 O2 4 2 L L D O2 / O D CO2 CO 2 2

(14) (15) (16)

However, it is known that reaction (1) is effective only under irradiation with wavelengths lower than 300 nm, where H2O2 absorption is important; as a black lamp seems to be used in the reported experiments, it is probable that some impurity, causing Fenton-type reactions (Fe or Cu ions) is the responsible for the improvement of As removal (see Section 2.2.6). If dissolved organic matter (DOM) is present in natural waters, H2O2 can be photochemically produced in-situ by the effect of solar light (Kocar and Inskeep, 2003): DOM D hn / DOM
L  DOM D O2 / DOMD D O 2 HO2 at acid pH

(9) (10) (11)

2HO 2 / H2 O2 D O2

Accordingly, Buschmann et al. (2005), using humic acid as representative of DOM, observed that the photooxidation rate of As(III) in air in the presence of UV light (366 nm) increased linearly with DOM concentration. This effect was much higher in the presence of Fe(III), due to a charge-transfer photochemical reaction forming HO or R from iron(III) hydroxo- or organocomplexes (Hug et al., 2001; Legrini et al., 1993; Litter, 2005; Zariou et al., 1984): FeIIIOH2D D hn / FeII D HO FeIIIRCO2 2D D hn / FeII D CO2 D R (12) (13)

Once H2O2 and Fe(II) are formed, the known Fenton reaction(7) takes place, generating more HO, and promoting a rapid As(III) oxidation (Litter, 2005). Khoe et al. (1997) and Zaw and Emett (2002) used iron salts and UV or solar light for oxidation of As(III) present in AMD liquid residues. Iron acts in these processes as both oxidant and coagulant; stable solids are formed that can be safely disposed. In 1996, a demonstration was carried out in an abandoned mine in Montana (USA) using two types of photoreactors: (a) plastic containers

Then, H2O2 and HO are formed, according to the above equations (11)(13) and (7). The Solar Oxidation and Removal of Arsenic method (SORAS) is a very simple process, used with partial success in poor, isolated populations in Bangladesh and India (Wegelin et al., 1994, 2000). In this method, contaminated water is put in transparent PET bottles of soft drinks or mineral water together with some drops of lemon juice (citric acid), and irradiated under sunlight for several hours. If there is enough iron in the waters, Fe(III)-citrate complexes are formed, and photo-Fenton processes take place, with the generation of oxidizing species. Then, As(III) is transformed to As(V) together with precipitation of iron(III) oxides/hydroxides, and As(V) adsorption and coprecipitation (Fig. 2, Hug et al., 1997; Hug and Leupin, 2003). During the night, bottles are put in a vertical position to promote settlement of the ocs and clear water is obtained by further decantation or ltration. Tests of this technology have been performed in Nicaragua, Bangladesh, Peru, Chile a and Argentina (Cornejo et al., 2008; Emett and Khoe, 2001; Garc et al., 2004; Hug, 2000; Hug et al., 2001; Hug and Leupin, 2003; nez Gonza lez, Lara et al., 2006; Litter, 2002, 2006; Litter and Jime 2004; Litter and Mansilla, 2003). However, groundwaters of several regions of LA do not have enough iron to make efcient the SORAS technology. To increase As removal, iron has to be added externally, in form of some natural Fe-containing minerals, iron wool, packing wire or zerovalent iron nanoparticles (Bundschuh et al., 2009; Litter et al., 2008; Morgada et al., 2008, 2009; Morgada de Boggio et al., 2009, in press). Commercial zerovalent iron nanoparticles exhibited outstanding properties to treat As-polluted groundwater of the Chaco-Pampean n province): As (around 200 mg L1) in plain of Argentina (Tucuma contact with these NZVI particles (0.025 g L1) was driven to levels in agreement with the regulations (<10 mg L1) after 3 h UV irradiation (Morgada et al., 2009; Morgada de Boggio et al., in press). Another possible photochemical process to oxidize As(III) in water is heterogeneous photocatalysis (HP), an Advanced Oxidation Technology that uses a particulate semiconductor, generally TiO2, for water detoxication (Bahnemann et al., 1994; Hoffmann et al., 1995; Legrini et al., 1993; Linsebigler et al., 1995; Litter, 1999, 2009; Mills and Le Hunte, 1997; Rajeshwar, 1995; Serpone et al., 1988). In HP, after excitation of TiO2 with UV light (energy equal to or higher than the TiO2 bandgap, Eg) conduction band electrons (e cb) and valence band holes (hvb) are created, which can recombine or migrate to the particle surface where they react with donor (D) or acceptor (A) species (Fig. 3). Couples with redox potentials more positive than that of e cb can be photocatalytically reduced and those with redox potentials more negative than the redox potential of h vb can be oxidized. For Degussa P-25, the most popular

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1113

A ecbh > Eg

cb

vb

hvb+

TiO2 particle
Fig. 2. Scheme of the SORAS process.

D +

Fig. 3. Simplied diagram of heterogeneous photocatalysis with TiO2 particles.

commercial form of photocatalytic TiO2, these values have been calculated as 0.3 and 2.9 V vs. NHE at pH 0, respectively (Martin et al., 2004); therefore, h vb are strong oxidants that may attack D directly or form hydroxyl radicals (HO) from water or surface hydroxide ions, while e cb are mild reducing acceptors. It has been established that HP processes under regular illumination take place only through monoelectronic steps. The above scheme can be described by the following simplied equations:
D TiO2 D hn / eL cb D hvb L eL cb D A / A  D hD vb D H2 O / HO D H D hD vb D D / D

(17) (18) (19) (20)

In particular, O2 can play the role of acceptor and it is reduced by    e cb to O2 , from which other ROS (HO2, H2O2 and nally HO ) are  formed, this being an alternative route of HO generation. Application of HP to the case of As(V) implies complex mecha nisms. Oxidation of As(III) can take place by h vb or HO , going rst to As(IV) and then to As(V):
 AsIII D hD vb =HO or other ROS / AsIV / AsV

(21)

bed, ow-through reactor for As(III) oxidation having TiO2 immobilized on glass beads (Ferguson and Hering, 2006). Nakajima et al. (2005) proposed the combined use of TiO2 as photocatalyst and activated alumina as adsorbent for the removal of inorganic As(III), MMA and DMA from aqueous media using Xe lamps or solar light. A low-cost HP procedure was proposed to remove As in well water samples of the Chaco-Pampean plain (Las Hermanas, Santiago del Estero province, Argentina). Walls of PET plastic bottles were internally impregnated with TiO2 by a very simple technique (Meichtry et al., 2007). When As-contaminated water samples (5001800 mg L1), poured into these bottles, were exposed to articial UV light in the presence of Fe(III) salts, more than 94% As removal took place (Bundschuh et al., 2009; Litter, 2006a,b; Litter et al., 2008; Mateu, 2007; Morgada et al., 2008; Morgada de Boggio et al., 2009, in press). Fostier et al. (2008) obtained similar results with laboratory samples under solar irradiation. According to the redox potential of TiO2 e cb, direct photocatalytic reduction of As(V) or As(III) is not thermodynamically possible, as proved by Yang et al. (1999) and conrmed by experiments with the stopped-ow technique using irradiated TiO2 nanoparticles (Litter et al., unpublished results). Nevertheless, TiO2 heterogeneous photocatalytic reduction of As(III)/(V) is indeed possible at acid pH by an indirect route in the presence of organic  donors. These donors are oxidized by h vb or HO in irreversible reactions, and produce strongly reducing radicals R, which in turn reduce arsenical species to elemental As:
  HRDhD vb =HO / R

Several examples of photocatalytic oxidation of As(III) by UV/ TiO2 at laboratory level are reported in the literature (Bissen et al., 2001; Dutta et al., 2005; Ferguson et al., 2005; Jayaweera et al., 2003; Lee and Choi, 2002; Leng et al., 2007; Ryu and Choi, 2004; Xu et al., 2005; Yang et al., 1999; Yoon et al., 2009). In all cases, As(III) oxidation was very rapid, taking place in time scales of 10 100 min at various concentrations (micromolar to millimolar range). Methylated arsenical compounds like monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) were easily degraded by UV-TiO2. Arsenate is the nal product for both MMA and DMA oxidation, with the consequent mineralization of the organic moiety of the arsenical initial species (Xu et al., 2007). A very interesting example is the use of an efcient, costeffective and environment-friendly adsorbent formed by a mixture of TiO2 and slag-iron oxide obtained from a municipal incinerator of solid wastes for photocatalytic oxidation of arsenite and simultaneous removal of the generated arsenate; the process was performed in a relatively short contact and illumination time (Zhang and Itoh, 2006). Another example is the design of a xed-

(22)

R D AsV=III / As0

(23)

The most common donors are methanol, ethanol or 2-propanol, which lead to 1-hydroxyalkyl radicals, while carboxylic acids generate strong reducing radicals such as CO 2 in the cases of formic or oxalic acids. This can be, then, a method to immobilize dissolved As in the form of the solid As(0) form. Combining photocatalytic oxidative and reductive pathways, Yang et al. (1999) proposed a two-step pollution abatement scheme: 1) initial oxidation of As(III) to As(V) either via UV/TiO2 or UV/H2O2, followed by 2) immobilization of As(V) as the elemental species on TiO2 in a second reductive stage, after adjustment of the efuent to acid pH. Other light-driven oxidative technologies have been tested. A UV light assisted process, which worked at neutral or alkaline pH,

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Table 2 Advantages and disadvantages of emergent technologies for arsenic removal. Technologies In-situ remediation (PRBs) Advantages Low operational costs. Low-cost local materials can be used. Disadvantages High impact of microbiological and geochemical processes at long term. Corrosion of materials. Permeability diminished by precipitation of suldes, oxides, hydroxides and carbonates. Produces toxic solid wastes. Complicate synthesis of material. Possible growth of microorganisms. Becomes clogged, if excessive iron. Much research still needed.

Zerovalent iron Zerovalent iron nanoparticles Geological materials as natural adsorbents Biological methods: bioadsorption, ex-situ bioleaching, phytoltration, phytoremediation Photochemical oxidative technologies: Fe salts/solar light, SORAS, TiO2 Heterogeneous Photocatalysis, ZVI, NZVI

Widely available local iron materials at low-cost. As(III) and As(V) can be treated. Higher contact surface results in a lower amount of iron. As(III) and As(V) can be treated. Feasible process in developing countries. Environmental compatibility and possible cost-effectiveness. Friendly and non-expensive technologies for poor and isolated populations. Based on the use of solar light and low-cost materials. Simultaneous oxidation of As and removal of natural organic pollutants, toxic metals and microbiological contamination can be achieved in most of the cases. Provides immobilized As(0) on TiO2.

External addition of iron to the waters before or after treatment is needed in LA.

Reductive TiO2 Heterogeneous Photocatalysis

Addition of organic donors and acid pH is required. Much research is still needed.

proposed the use of sulte or another oxidizable sulfur form as photoabsorber (Khoe et al., 1998; Zaw and Emett, 2002). Photochemical As(III) oxidation by combined vacuum-UV and short UV irradiation (185 and 254 nm) was recently investigated (Yoon et al., 2008). The method proved to be better than other photooxidation procedures (e.g., UV-C/H2O2, UV-A/Fe(III)/H2O2 and UV-A/TiO2), transforming 100 mM As(III) almost completely in 10 min. The reaction occurs through HO produced by 185 nm photosplitting of water (H2O / H HO), and it is enhanced by the presence of Fe(III) and H2O2. The method was also effective to oxidize As(III) in a real natural water. Adsorption on activated alumina or coagulation/precipitation with FeCl3 was used to remove the produced As(V). Neppolian et al. (2008) described a very rapid photochemical As(III) oxidation using low amounts of potassium peroxydisulfate (K2S2O8). The oxidant was proposed to be the sulfate radical (SO 4 ). Recently, Yeo and Choi (2009) studied the reaction of arsenite under 254 nm irradiation mediated by iodide, nding quantitative oxidation to As(V). The authors suggest that the process could be applied in treatment plants for acid waters polluted with As in the range 11000 mg L1 and higher, employing directly the already existing germicide lamps in these plants. 2.2.7. Comparison of emergent technologies In Table 2 are listed the main advantages and disadvantages of emergent technologies for arsenic removal cited in this work.

cost technologies using non-expensive materials, sunlight or biological methods should be developed. However, further research is needed to nd additional methods and to assess the effectiveness of the proposed technologies. In each case, the validation of the method with real waters of the site before application is mandatory. Arsenic removal from water for human consumption seems to be a very difcult task. Not a universal method exists and the election is very dependent on the composition of waters to be treated. Socioeconomic features should be carefully taken into account to select the technology. The problem of As in LA is of the same order of magnitude as in other world regions, such as SE Asia, but it is often not described in English. Although various studies have been undertaken by numerous local researchers, and proven treatment methods for the specic water conditions have been encountered, technologies have been not yet commercialized due to a lack of interest of authorities, local industries and international agencies for nancial and technical cooperation. Acknowledgements This work was performed as part of Agencia Nacional de Pro n Cient ca y Tecnolo gica PICT-512 and CYTED 406RT0282 mocio Thematic Network. References
n-Herrera, M.T., Nu n rquez, ez-Montoya, O.G., Melgoza-Castillo, A., Royo-Ma Alarco M.H., Rodriguez Almeida, F.A., 2009. Potential use of sedges (Cyperaceae) in arsenic phytoremediation. In: Bundschuh, J., Armienta, M.A., Birkle, P., Bhattacharya, P., Matschullat, J., Mukherjee, A.B. (Eds.), Geogenic Arsenic in Groundwater of Latin America. In: Bundschuh, J., Bhattacharya, P. (Series Eds.), Arsenic in the Environment, vol. 1. CRC Press/Balkema Publisher, Leiden, The Netherlands, pp. 649655. dez, M., Lue -Meru , M.P., Graterol, N., Anzalone, A., Arroyo, C.J., Alvarado, S., Gue ray, G., 2008. Arsenic removal from water by bioremediation with the aquatic Za plants water hyacinth (Eichornia crassipes) and Lesser Duckweed (Lemna minor). Bioresource Technology 99, 84368440. rez-Garibay, R., 2009. AdsorpAlvarez-Silva, M., Uribe-Salas, A., Nava-Alonso, F., Pe tion of As(V) onto goethite: experimental statistical optimization. In: Bundschuh, J., Armienta, M.A., Bhattacharya, P., Matschullat, J., Birkle, P., Mukherjee, A.B. (Eds.), Geogenic Arsenic in Groundwater of Latin America. In: Bundschuh, J., Bhattacharya, P. (Series Eds.) Interdisciplinary Books Arsenic in the Environment, vol. 1. CRC Press/Balkema Publishers, Lisse, The Netherlands. pp. 527534.

3. Conclusions Arsenic occurs in natural waters predominantly in inorganic forms, such as arsenite (As(III)) and arsenate (As(V)). The presence of arsenic in water for human consumption causes the appearance of HACRE, an endemic illness, affecting a large number of people in LA. As(V) is more effectively removed from source waters than As(III) by iron coagulants, by precipitation of natural iron, and by adsorptive media. To remove As(III), a previous oxidation to As(V) is needed. Conventional technologies (coagulationcoprecipitation, adsorption, reverse osmosis, etc.) can be applied at medium or large scale. However, for domestic or community purposes as those frequently found in rural or urban isolated population in LA, low-

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Abbreviations
A: acceptor ALUFLOC: a household scale low-cost As removal methodology AMD: acid mine drainage ARCIS-UNR: process developed by the Center of Sanitary Engineering of the National University of Rosario CI: capacitive deionization CYTED: Science and Technology for the Development D: donor DMA: dimethylarsinic acid DOM: dissolved organic matter ED: electrodialysis EDR: electrodialysis with reversion of polarity of the electrodes EPA: Environmental Protection Agency GFH: granular iron hydroxide GFO: granular iron oxide HACRE: Chronic Endemic Regional Hydroarsenicism HAPb: Natural biogenic hydroxyapatite HP: heterogeneous photocatalysis HR-XPS: High Resolution X-Ray Photoelectronic Spectroscopy IARC: International Agency for Research on Cancer iAs: inorganic arsenic IBEROARSEN: Iberoamerican CYTED Network LA: Latin America MF: microltration MMA: monomethylarsonic acid NF: nanoltration NZVI: nanoparticulate ZVI PAC: polyaluminum chloride PRB: permeable reactive barriers RO: reverse osmosis SORAS: Solar Oxidation and Removal of Arsenic SS: suspended solids TDS: total dissolved solids UF: ultraltration WHO: World Health Organization ZVI: zerovalent iron